CN104271657A - Carbinol-terminated polymers containing amine - Google Patents
Carbinol-terminated polymers containing amine Download PDFInfo
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- CN104271657A CN104271657A CN201380024018.9A CN201380024018A CN104271657A CN 104271657 A CN104271657 A CN 104271657A CN 201380024018 A CN201380024018 A CN 201380024018A CN 104271657 A CN104271657 A CN 104271657A
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- FDTCKQAXTOUSOP-UHFFFAOYSA-N CC1C[Si](C)(C)OC1 Chemical compound CC1C[Si](C)(C)OC1 FDTCKQAXTOUSOP-UHFFFAOYSA-N 0.000 description 1
- LFTRYJGXQHFPCE-UHFFFAOYSA-N C[Si]1(C)OCCOC1 Chemical compound C[Si]1(C)OCCOC1 LFTRYJGXQHFPCE-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
Abstract
The invention relates to diene polymers having, at the start of the polymer chain, tertiary amino groups of formula (I) or (II), wherein R1, R2 are identical or different and represent alkyl-, cycloalkyl-, aryl-, alkaryl- and aralkyl groups which can contain heteroatoms such as O, N, S and/or Si, Z represents a divalent organic group, which can also contain, in addition to C and H, heteroatoms such as O, N, S and/or Si, and, on the polymer chain ends, silane-containing carbinol groups of formula (III) or the metal salts thereof or the semi-metal salts thereof, wherein R3, R4, R5, R6 are identical or different and represent H, alkyl-, cycloalkyl-, aryl-, alkaryl- and aralkyl groups which can contain heteroatoms such as O, N, S and/or Si, A represents a divalent organic group which can also contain, in addition to C and H, heteroatoms such as O, N, S and/or Si.
Description
The present invention relates to the diene polymer of the top at polymer chain and the end-functionalization at polymer chain and preparation thereof and purposes.
Key property desired in tire tread is included in tack good on dry surface and wet structure and high wear resistance.Improve a kind of sliding resistance of tire and asynchronously weaken rolling resistance and wear resistance is very difficult.Low-rolling-resistance is important for low fuel consumption, and high-wearing feature is a crucial factor for long lifetime of tire.
The wet and slippery dynamic resistance of tire tread and rolling resistance depend on to a great extent for the production of mixture rubber dynamic/mechanical property.For reducing rolling resistance, under tire tread is used in higher temperature, (60 DEG C to 100 DEG C) have elastomeric rubber.Another aspect, the rubber that (0 DEG C to 23 DEG C) has the high damping factor or have a low elasticity within the scope of 0 DEG C to 23 DEG C is at low temperatures favourable for the wet and slippery dynamic resistance of reduction.In order to meet the compound characteristics that these require, the mixture of various different rubber is used to this tyre surface.Usually, the mixture used is that one or more have the rubber of relatively high second-order transition temperature, as styrene butadiene rubbers, with one or more, there is the rubber of lower second-order transition temperature, as high by 1 in having, the polyhutadiene of 4-cis-content or have low-styrene and low vinyl content styrene butadiene rubbers or a kind of prepare in the solution and there is the Isosorbide-5-Nitrae-cis of appropriateness and the polyhutadiene of low vinyl content.
The solution rubber of the anionoid polymerization containing double bond, such as solution polyhutadiene and solution styrene-butadiene rubber, have the advantage surmounting corresponding emulsion rubber for the tire tread that production has low-rolling-resistance.These advantages are especially the controllability of contents of ethylene and the second-order transition temperature be associated and branchign of molecule.In actual use, unique advantage is created in this relation just between the resistance to wet skidding performance of tire and rolling resistance.Therefore the significant contribution of rolling resistance is come to formation and the degraded of the free end of polymer chain and the reversible of filler network to the waste of energy of tire tread, this filler network is formed (being generally silica and/or carbon black) by the filler for tire tread compounds.
The end of the top of polymer chain and/or polymer chain introduce functional group enable the top of chain and/or the end of chain filling surface produce physics or the attachment of chemistry.Which has limited its movability, and therefore reduce the waste of energy of tire tread under Dynamical stress effect.Meanwhile, these functional groups can improve the dispersion of filler in tire tread, thus cause weakening and therefore causing rolling resistance to reduce further of filler network.
Description is had in the literature in the method for the top of polymer chain introducing functional group by function anionic polymerization initiator; such as; in EP 0 513 217 B1 and EP 0 675 140 B1 (initiator with shielded hydroxyl); US 2008/0308204 A1 (initiator containing thioether) and US 5; 792,820 and EP 0 590 490 B1 (alkali metal compound of secondary amine is as polymerization starter) in.
More particularly, EP 0 594 107 B1 describes secondary amine as the use in position of function polymerization starter, but does not describe the end of the chain functionalization of polymkeric substance.
In addition, many methods for introducing functional group at the end of polymer chain have been developed.Such as, EP 0 180 141 A1 describes use 4,4 '-bis-(dimethylin) benzophenone or N-methyl caprolactam as functionalized reagent.The use of oxyethane and N-vinyl pyrrole pyridine ketone is known from EP 0 864 606 A1.Multiple functionalized reagent possible in addition at US 4,417, have detailed description in 029.
Especially silicon has total at least two halogenic substituents and/or alkoxy substituent and/or the chain end functionalization of the substituent silane of aryloxy to dience rubber polymkeric substance and have good applicability, because on the silicon atoms one of described substituting group can easily with the negatively charged ion diene polymer end of the chain exchange and on Si other one or more above-mentioned substituting group can be used as a kind of functional group, this functional group, after being optionally hydrolyzed, can interact with the filler of tire tread compounds.The example of such silane can at US 3, and 244,664, find in US 4,185,042, EP 0 890 580 A1.
But, mention, have shortcoming for multiple in the reagent of the end-functionalized of polymer chain, such as, in process solvent poorly soluble, toxicity is large or volatility large, and this can cause the pollution of recovered solvent.In addition, multiple in described functionalized reagent can with more than one anionic polymer chain end reaction, this causes troublesome often and unmanageable linked reaction.This is especially true for the silane mentioned.These have other shortcoming equally: the composition as halogenide or alkoxy base is eliminated in the reaction of the negatively charged ion end of described silane and polymer chain, and the latter is easy to be converted to alcohol.Halogenide promotes corrosion; Alcohol can cause the pollution processing solvent.Silane is used to be as the other shortcoming of functionalized reagent, the polymkeric substance of the siloxane blocking be made up of it, passing through Si-OR group (or by the Si-OH group after the hydrolysis of Si-OR group) after polymkeric substance chain end functionalization, coupling can form Si-O-Si key, this causes the undesirable rising in processing and storage process in rubber viscosity.Describe multiple for reducing the method that described viscosity increases when the polymkeric substance of siloxane blocking, such as, added based on the stabilizing agent (EP 0 801 078 A1) of acid and acyl halide, the reagent (EP 1 726 598) that adds siloxanes (EP 1 198 506 B1), add the alcohol (EP 1 237 934 B1) of long-chain or add for control pH.
Cyclosiloxane is described as by EP 0 778 311 B1, among other things, introduces the functionalized reagent of Si-OH group in the end of polymer chain.Described cyclosiloxane has following advantage than above-mentioned silane: each siloxane molecule is only to react with there being a negatively charged ion end of this polymer chain in each case.Therefore, although each functionalized reagent increases more than one polymer chain, in reaction kinetic, coupling is not had to occur.But, introducing this Si-OH end group formed after functionalized reagent, as described above and also have at US 4,618, described in 650, can coupling formation Si-O-Si key.Therefore the undesirable rising problem in processing and storage medium viscosity is also had here.
Therefore, an object of the present invention is to provide the polymkeric substance of the functionalization of the defect not having prior art, and make it possible to utilization more specifically and there is polymer chain negatively charged ion end and the sound response that do not have the silane of its shortcoming (reaction of several negatively charged ion ends of several polymer chains of each silane molecule in such as process and storage process, the elimination reaction of trouble component and the Coupled-reaction of formation Si-O-Si key).
For achieving this end, propose the diene polymer of functionalization, described diene polymer has the tertiary amine group of chemical formula for (I) or (II) at the top of polymer chain
Or
Wherein
R
1, R
2identical or different, and each naturally may containing heteroatoms as the alkyl of O, N, S and/or Si, cycloalkyl, aryl, alkaryl and aromatic alkyl group,
Z is the organic group of a divalence, and this organic group can also comprise heteroatoms except C and H, as O, N, S and/or Si,
Further, at the end of polymer chain, there is the methanol-based containing silane that chemical formula is (III)
Or its metal-salt or its semi-metal salt, wherein
R
3, R
4, R
5, R
6identical or different, and each H naturally or may containing heteroatoms as the alkyl of O, N, S and/or Si, cycloalkyl, aryl, alkaryl and aromatic alkyl group,
A is the organic group of a divalence, and this organic group can also comprise heteroatoms except C and H, as O, N, S and/or Si.
Preferably, the end of the polymer chain of the diene polymer of functionalization of the present invention, chemical formula be (III), can should exist with the metallic salt form of chemical formula (IV) containing methanol-based of silane:
Wherein
R
3, R
4, R
5, R
6identical or different, and each H naturally, may containing heteroatoms as the alkyl of O, N, S and/or Si, cycloalkyl, aryl, alkaryl and aromatic alkyl group,
A is the organic group of a divalence, and this organic group can also comprise heteroatoms except C and H, as O, N, S and/or Si,
N is the integer from 1 to 4,
M to be valency be 1 to 4 a kind of metal or semi-metal, preferred Li, Na, K, Mg, Ca, Fe, Co, Ni, Al, Nd, Ti, Si and/or Sn.
Polymkeric substance preferably for the preparation of the diene polymer of functionalization of the present invention is diene polymer, and the diene copolymers obtained by diene and vinyl aromatic monomers interpolymerization.
Preferred diene is 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadienes, 1-phenyl-1,3-butadiene and/or 1,3-hexadiene.Particularly preferably be and use 1,3-butadiene and/or isoprene.
Such as, this vinyl aromatic co-monomers can be vinylbenzene, adjacent, and/or p-methylstyrene, p-tert-butylstyrene, alpha-methyl styrene, vinyl naphthalene, Vinylstyrene, trivinylbenzene and/or divinyl naphthalene.Particularly preferably be use vinylbenzene.
These polymkeric substance are preferably by anionic solution polymerization reaction preparation.
The initiator of anionic solution polymerization reaction is the alkali metal amide of secondary organic amine, such as: pyrrole amides lithium, piperidine amides lithium, hexamethylene imine lithium (lithium hexamethyleneimide), 1-methyl imidazolidinone acid amides lithium, 1-methylpiperazine acid amides lithium, morpholino amide lithium, diphenyl amide lithium, dibenzyl base acid amides lithium, dicyclohexyl acid amides lithium, dihexyl acid amides lithium, dioctyl acid amides lithium.In addition, also dual functional alkali metal amide can be used, such as, piperazine amide two lithium.
These alkali metal amides are prepared preferably by the reaction of corresponding secondary amine and organic alkali metal compound.Preferred organic alkali metal compound is n-Butyl Lithium and s-butyl lithium for this purpose.This alkali metal amide is preferably prepared by the reaction original position of a kind of organic alkali metal compound and secondary amine in polymerization reactor.Preferred secondary amine is Pyrrolizidine, piperidines, hexamethylene imine, 1-alkyl imidazoline, 1-alkylpiperazine, morpholine, N, N-pentanoic, N, N-dibenzylamine, N, N-dicyclohexyl amine, N, N-dihexylamine, N, N-Di-Octyl amine.
In addition, randomizer and the control agent of the known microtexture for polymkeric substance can be used, such as diethyl ether, diη-propyl ether, Di Iso Propyl Ether, di-n-butyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate n-butyl ether, ethylene glycol bisthioglycolate tertbutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol di-n-butyl ether, Diethylene Glycol di-tert-butyl ether, 2-(2-ethoxy ethoxy)-2-methylpropane, TRIGLYME, tetrahydrofuran (THF), ethyltetrahydrofuran base ether, hexyl tetrahydrofuran base ether, 2, two (2-tetrahydrofuran base) propane of 2-, dioxane, Trimethylamine 99, triethylamine, N, N, N ', N '-tetramethylethylened, N-methylmorpholine, N-ethylmorpholine, 1, 2-dipiperidino ethane, 1, 2-dipyrryl ethane, 1, 2-dimorpholine base ethane, and alcohol, phenol, carboxylic acid, the potassium of sulfonic acid and sodium salt.
Such solution polymerization be known and, such as, be described in I.Franta, elastomerics and rubber compounded materials (Elastomers and Rubber Compounding Materials); Elsevier 1989,113-131 page, Houben-Weyl, Methoden der Organischen Chemie [organic chemistry procedures], Thieme Verlag, Stuttgart, 1961, volume XIV/1,645 to 673 pages or volume E 20 (1987), 114 to 134 pages and 134 to 153 pages and also have comprehensive polymer science (Comprehensive Polymer Science), volume 3, part i (Pergamon Press Ltd., Oxford 1989), 365-386 page.
Prepare preferred diene polymer preferably to carry out in a solvent.Solvent for polyreaction is preferably inert aprotic solvent, such as paraffinic, as isomeric butane, pentane, hexane, heptane, octane, decane, pentamethylene, hexanaphthene, methylcyclohexane, ethylcyclohexane or 1,4-dimethyl cyclohexane or aromatic hydrocarbon based, as benzene, toluene, ethylbenzene, dimethylbenzene, diethylbenzene or propyl benzene.These solvents can individually or combinationally use.Preferably hexanaphthene and normal hexane.Equally likely blended with polar solvent.
100g to 1000g, preferably 200g to 700g is generally based on the total usage quantity of monomer of 100g according to the amount of the solvent in method of the present invention.But, also likely when there is not solvent, used monomer is polymerized.
This polyreaction can be carried out in such a way, and which is make monomer, the control agent optionally adjusting microtexture and solvent by initially filler and then add initiator to start polymerization.It is also possible for being polymerized in fill process, in this process, polymerization reactor is filled by the monomer that adds, the control agent optionally adjusting microtexture and solvent, and this initiator adds by initially filler or along with monomer, the control agent optionally adjusting microtexture and this solvent.Change is possible, as by solvent initial fillers in reactor, add initiator and then add monomer and optionally adjust the control agent of microtexture.In addition, this polyreaction can be carried out in a continuous manner.In all cases, the other increase in the process of polyreaction or at the end of polyreaction of monomer, control agent and solvent is possible.
In a preferred embodiment, this monomer, the control agent optionally adjusting microtexture, this solvent and a kind of secondary amine are by initially filler, and this polyreaction is by adding a kind of organic alkali metal compound, as BuLi, start along with reacting by organic alkali metal compound and secondary amine the initiator forming alkali metal amide in position.
This polymerization reaction time can change from several minutes to several hours in very wide scope.Usually, this polyreaction minute to be carried out to 8 hours, preferably 20 at about 10 minutes to the period of 4 hours.This polyreaction can be carried out under standard pressure or under the pressure raised (1 to 10 bar).
Have been found that, surprisingly, introduce tertiary amine group by using alkali metal amide polymerization starter at the top of polymer chain and one or more 1-oxa-s of conbined usage-2-sila naphthenic hydrocarbon as the functionalized reagent for introducing functional group at the end of polymer chain, the tire tread performance and the diene polymer not having defect of the prior art with improvement can be prepared.Such as, by the linked reaction of the multiple reaction of functionalized reagent, have the elimination reaction of problem composition and by process (workup) and the linked reaction forming Si-O-Si key in storage process can not occur.
The compound of this alkali metal amide polymerization starter to be general formula be (V) or (VI)
Or
Wherein
R
1, R
2identical or different, and each naturally may containing heteroatoms as the alkyl of O, N, S and/or Si, cycloalkyl, aryl, alkaryl and aromatic alkyl group,
Z is the organic group of a divalence, and this organic group can also comprise heteroatoms except C and H, as O, N, S and/or Si,
M is Li, Na, K.
This 1-oxa--2-sila naphthenic hydrocarbon is the compound with following general formula (VII)
Wherein
R
3, R
4, R
5, R
6identical or different, and each H naturally, may containing heteroatoms as the alkyl of O, N, S and/or Si, cycloalkyl, aryl, alkaryl and aromatic alkyl group,
A is the organic group of a divalence, and this organic group can also comprise heteroatoms except C and H, as O, N, S and/or Si.
The Si atom with chemical formula (VII) is simple function, and " simple function " is interpreted as and refers to that this Si atom has three Si-C keys and a Si-O key.
The example with the compound of chemical formula (VII) is:
2,2-dimethyl-1-oxa--2-Silinane
2,2-diethyl-1-oxa--2-Silinane
2,2-dipropyl-1-oxa--2-Silinane
2-methyl-2-phenyl-1-oxa--2-Silinane
2,2-phenylbenzene-1-oxa--2-Silinane
2,2,5,5-tetramethyl--1-oxa--2-Silinane
2,2,3-trimethylammonium-1-oxa--2-Silinane
2,2-dimethyl-1-oxa--2-silacyclopentan
2,2,4-trimethylammonium-1-oxa--2-silacyclopentan
2,2-dimethyl-Isosorbide-5-Nitrae-dioxa-2-Silinane
2,2,5,5-tetramethyl--Isosorbide-5-Nitrae-dioxa-2,5-bis-Silinane
2,2,4-trimethylammonium-[Isosorbide-5-Nitrae, 2] silicon is for morpholine
Benzo-2,2-dimethyl-Isosorbide-5-Nitrae-dioxa-2-Silinane
Benzo-2,2,4-trimethylammonium-1-oxa--4-azepine-2-Silinane
Have been found that the diene polymer of functionalization of the present invention can be reacted by the reactive terminal of polymer chain and 1-oxa--2-sila naphthenic hydrocarbon and the protonation of optionally alkoxide end group is subsequently prepared to provide alcohol.
Therefore, the present invention also specify 1-oxa--2-sila naphthenic hydrocarbon as functionalized reagent preparation functionalization of the present invention, purposes in the diene polymer with chemical formula (III) or (IV) end group.
It is 10 000 grams/mol to 2 000 000 grams/mol that the diene polymer of functionalization of the present invention preferably has average molar mass (number is average), preferably 100 000 grams/mol to 1,000 000 grams/mol, and second-order transition temperature is-110 DEG C to+20 DEG C, preferably-110 DEG C to 0 DEG C, and mooney viscosity ML 1+4 (100 DEG C) is 10 to 200, preferably 30 to 150, mooney unit.
The present invention also provides the method for the diene polymer preparing functionalization of the present invention, according to the secondary organic amine of a kind of this method alkali metal amide is used as polymerization starter, one or more chemical formulas are the compound of (VII), the reactive terminal of a kind of pure substance, solution or suspension and polymer chain is reacted.The compound that chemical formula is (VII) is preferably added into after polyreaction terminates, but they also can be added into before complete monomer conversion.Carry out at the temperature that the reaction that chemical formula is the compound of (VII) and the reactive terminal of polymer chain is commonly used in polyreaction.Reaction times for the reaction according to the compound of chemical formula (VII) and the reactive terminal of this polymer chain can between several minutes to a few hours.
The alkali metal amide used preferably in the solution.Give preferably to use the same solvent also used in the polymerization.But the solvent mixture that also can use solvent or have relatively high polarity is to prevent the precipitation of this alkali metal amide.
A kind of preferably method preparing the diene polymer of functionalization of the present invention, in the method this polymerization starter be by secondary amine and organic alkali metal compound a preliminary forming step be separated or in the polymerization reactor forming alkali metal amide direct in-situ react and obtain, and the compound being (VII) by one or more chemical formulas is used as a kind of pure substance, solution or suspension to react with the reactive terminal of this polymer chain.The compound that chemical formula is (VII) is preferably added into after polyreaction terminates, but they also can be added into before complete monomer conversion.Carry out at the temperature that the reaction that chemical formula is the compound of (VII) and the reactive terminal of polymer chain is commonly used in polyreaction.Reaction times for the reaction according to the compound of chemical formula (VII) and the reactive terminal of this polymer chain can between several minutes to a few hours.
The amount of secondary amine is preferably less than or equal to the amount of organic alkali metal compound, and the mol ratio specifically preferably between secondary amine and organic alkali metal compound is 0.05-2.00:0.05-2.00.
Have been found that, with this ratio, the end of polymer chain is by the methanol-based compound functionalization containing silane, thus form the polymkeric substance with the tire tread performance of improvement of two ends functionalization, avoid the coupling of the multiple reaction by functionalized reagent simultaneously, have the elimination reaction of problem composition and by the reaction and form the coupling of Si-O-Si key in the storage process of polymkeric substance.
The amount of 1-oxa--2-sila naphthenic hydrocarbon that chemical formula is (VII) can be selected like this: the reactive end of all polymer chains is all that the compound of (VII) reacts with chemical formula, maybe can use described compound in shortage.The chemical formula used is that the amount of the compound of (VII) can cover very wide scope.Based on the amount of polymkeric substance, preferred amount is between 0.005% to 2% by weight, is preferredly by weight between 0.01% to 1%.
Except the compound that chemical formula is (VII), the reactive end of typical negatively charged ion diene polymer coupling reagent and polymer chain also can be used to react.The example of such coupling reagent is silicon tetrachloride, METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), tin tetrachloride, dibutyltin dichloride, tetraalkoxysilane, ethylene glycol bisthioglycolate glyceryl ether, 1,2,4-tri-(chloromethyl) benzene.These coupling reagents can before the compound with chemical formula (VII), add together with them or after them.
After chemical formula is the compound of (VII) and optional coupling reagent has added, before the process of functionalized polymer of the present invention or period, preferably add conventional aging stabilizer, as sterically hindered phenol, aromatic amine, phosphorous acid ester, thioether.In addition, the conventional increment oils for elastoprene can be added, such as DAE (distillation aromatic series extract), TDAE (treated distillation aromatic series extract), MES (solvate of gentle extraction), RAE (residue aromatic series extract), (naphthenic) of TRAE (treated residue aromatic series extract), cycloalkanes and the finish class of heavy cycloalkanes.Also likely add weighting agent, as carbon black and silica, rubber and rubber ingredients.
This solvent by conventional method as distillation, steam stripped or application of reduced pressure, optionally at elevated temperatures, can remove from polymerization process.
The present invention also specify the purposes of functionalized polymer of the present invention in production curable rubber compositions.
Described curable rubber compositions preferably includes other rubber, weighting agent, rubber chemicals product, processing aid and extending oil.
Other rubber such as, is natural rubber and synthetic rubber.If existed, its amount based on the polymkeric substance in mixture total amount by weight preferred scope be from 0.5% to 95%, preferably 10% to 80%.The amount of the rubber of extra interpolation is still guidance by the end-use of the correspondence of mixture of the present invention.
This is set forth in by way of example from known in the literature synthetic rubber.They, except other things, comprise,
BR-polyhutadiene
ABR-divinyl/C
1-C
4alkyl acrylate copolymer
IR-polyisoprene
That E-SBR-is prepared by emulsion polymerization, cinnamic content is the styrene-butadiene copolymer of 1%-60%, preferably 20%-50% by weight
That S-SBR-is prepared by solution polymerization, cinnamic content is the styrene-butadiene copolymer of 1%-60%, preferably 15%-45% by weight
IIR-isobutylene-isoprene copolymer
The content of NBR-vinyl cyanide is by weight for 5%-60%, the preferably butadiene-acrylonitrile of 10%-40% are multipolymers
The NBR rubber of HNBR-partial hydrogenation or all hydrogenation
EPDM-Ethylene-Propylene-Diene trimer
And the mixture of these rubber.For the production of vehicle tyre, specifically interested be natural rubber, E-SBR and S-SBR of second-order transition temperature higher than-60 DEG C, the polybutadiene rubber with high cis-contents (>90%) by the catalyst preparing based on Ni, Co, Ti or Nd and there is polybutadiene rubber and their mixture of the contents of ethylene being up to 80%.
The effective weighting agent of rubber combination of the present invention comprises all known weighting agents for rubber industry.These include both weighting agents of activity and inertia.
Should mention by way of example following these:
-particulate silicon-dioxide, such as, by what produce from the precipitin reaction of silicate solutions or the flame hydrolysis of silicon halide, has 5m
2/ g to 1000m
2/ g, preferably 20m
2/ g to 400m
2the specific surface area (BET surface-area) of/g, and there is the primary particle diameter of 10nm to 400nm.These silicas optionally can also with other metal oxides, as the oxide compound of Al, Mg, Ca, Ba, Zn, Zr, Ti, mixed oxide form exist;
The silicates of-synthesis, as pure aluminium silicate, alkaline earth metal silicate (as Magnesium Silicate q-agent or Calucium Silicate powder), has from 20m
2/ g to 400m
2the BET surface-area of/g and the primary particle size from 10nm to 400nm;
-natural silicate, such as kaolin and other naturally occurring silicas;
-glass fibre and glass fibre product (felt, rope strand) or glass microballon grain;
-metal oxide, such as zinc oxide, calcium oxide, magnesium oxide, aluminum oxide;
-metal carbonate, such as magnesiumcarbonate, calcium carbonate, zinc carbonate;
-metal hydroxides, such as aluminium hydroxide, magnesium hydroxide;
-metal sulfate salt, such as calcium sulfate, barium sulfate;
-carbon black: have carbon black to be used to be standby by flame-carbon black method, channel process-carbon black method, stove-carbon black method, gas-carbon black method, pyrolysis-carbon black method or acetylene-carbon black method or photoelectric arc legal system at this and there is 9m
2/ g to 200m
2the carbon black of the BET surface-area of/g, such as SAF, ISAF-LS, ISAF-HM, ISAF-LM, ISAF-HS, CF, SCF, HAF-LS, HAF, HAF-HS, FF-HS, SRF, XCF, FEF-LS, FEF, FEF-HS, GPF-HS, GPF, APF, SRF-LS, SRF-LM, SRF-HS, SRF-HM and MT carbon black, or the N110 of ASTM, N219, N220, N231, N234, N242, N294, N326, N327, N330, N332, N339, N347, N351, N356, N358, N375, N472, N539, N550, N568, N650, N660, N754, N762, N765, N774, N787 and N990 carbon black,
-rubber gels, particularly based on BR, E-SBR and/or sovprene, those of particle diameter with 5nm to 1000nm.
The weighting agent used is preferably fine particle silica and/or carbon black.
Mentioned weighting agent can be used alone or uses with mixture.In a good especially embodiment, this rubber combination comprises a kind of mixture be made up of weighting agent (as fine-particle silicon dioxide) and the carbon black of light color as weighting agent, the weighting agent of light color and the ratio of mixture of carbon black are from 0.01:1 to 50:1, preferably from 0.05:1 to 20:1.
Based on the rubber of 100 weight parts by weight, the amount of weighting agent is by weight in the scope from 10 to 500 weight parts as used herein.Preferably use from 20 to 200 weight parts.
In yet another embodiment of the present invention, this rubber combination also comprises rubber ingredients, these rubber ingredients, such as, improve the processing characteristics of this rubber combination, crosslinked for rubber combination, improve the physicals for its specific end-use of the curing rubber manufactured by rubber combination of the present invention, improve interaction between rubber and weighting agent or for the attachment of rubber to weighting agent.
Such as, rubber ingredients are: linking agent class (as sulphur or for sulphur compound), and also have reaction promotor class, aging stabilizer class, thermo-stabilizer class, light stabilizers, antiozonidate class, processing aid class, softening agent class, tackifier class, whipping agent class, dye class, pigment class, wax class, extender class, organic acid, silicane, retarding agent class, metal oxide-type, extender oils, as DAE (distillation aromatic series extract), TDAE (treated distillation aromatic series extract), MES (solvate of gentle extraction), RAE (residue aromatic series extract), TRAE (treated residue aromatic series extract), the finish class of cycloalkanes and heavy cycloalkanes and activator class.
Based on 100 weight parts of the weighing scale by total rubber, the total amount of rubber ingredients is by weight in the scope from 1 to 300 weight part.Preferably use the rubber ingredients of 5 to 150 weight parts.
This curable rubber compositions can in single phase method or prepare in multistage method, preferably 2 to 3 mix stages.Such as, the mix stages that sulphur can be separated at promotor adds, such as, at cylinder, preferred temperature at 30 DEG C within the scope of 90 DEG C.Preferably by sulphur and promotor in the end mix stages add.
The example being suitable for the assembly preparing this curable rubber compositions comprises roller, kneader, Banbury mixer or mixing forcing machine.
Therefore, the present invention also provides curable rubber compositions, and the top that these curable rubber compositions are included in polymer chain has tertiary amine group that chemical formula is (I) or (II) and has the diene polymer of the functionalization of the functional group that chemical formula is (III) or (IV) at the end of polymer chain.
This rubber combination can also comprise the diene polymer of functionalization, this diene polymer has the tertiary amine group that chemical formula is (I) or (II) at the top of polymer chain, and has the functional group of chemical formula for (III) and (IV) at the end of polymer chain.
Present invention also offers curable rubber compositions of the present invention and especially produce tire at production curing rubber, especially produce the purposes had in the tire tread of rolling resistance low especially and high humidity sliding resistance and high-wearing feature.
Curable rubber compositions of the present invention is also suitable for producing moulded product, such as, produce following article: cable sheath, flexible pipe, pulley belt, travelling belt, pressure roller coating, sole, sealing-ring and damper assembly.
Following instance for illustration of the present invention, but does not have restricted effect.
example
example 1a: synthesis does not have the styrene-butadiene copolymer (comparison example) of functionalization
8.5kg hexane, 1185g 1 is filled in the reactor of the 20L of an inerting, 3-divinyl, 315g vinylbenzene, 8mmol 2, the n-Butyl Lithium of two (2-tetrahydrofuran base) propane of 2-and 10.3mmol, and these weighting materials are heated to 65 DEG C.Polyreaction carries out lasting 25 minutes under stirring at 65 DEG C.Subsequently, add 10.3mmol hexadecyl alcohol, this rubber solutions is discharged and passes through to add 3g's
1520 (two (octyl group the thiomethyl)-6-methylphenols of 2,4-) make it stablize, and by steam stripped by this solvent removal.By this buffings under reduced pressure 65 DEG C of dryings.
Contents of ethylene (IR spectrography): by weight 50.2%; Styrene content (IR spectrography): by weight 20.9%, second-order transition temperature (DSC) :-25.6 DEG C; Mumber average molar mass M
n(GPC, PS standard): 258kg/mol; M
w/ M
n: 1.15; Mooney viscosity (ML 1+4, at 100 DEG C): 52ME
example 1b: synthesize the styrene-butadiene copolymer at the top of chain with tertiary amine group (right
than example)
8.5kg hexane, 1185g 1 is filled in the reactor of the 20L of an inerting, 3-divinyl, 315g vinylbenzene, 11.3mmol 2,2-bis-(2-tetrahydrofuran base) propane, 14.1mmol Pyrrolizidine and 14.1mmol n-Butyl Lithium, and these weighting materials are heated to 65 DEG C.Polyreaction carries out lasting 25 minutes under stirring at 65 DEG C.Subsequently, add 14.1mmol hexadecyl alcohol, this rubber solutions is discharged and passes through to add 3g's
1520 make it stablize, and by steam stripped by this solvent removal.By this buffings under reduced pressure 65 DEG C of dryings.
Contents of ethylene (IR spectrography): by weight 50.0%; Styrene content (IR spectrography): by weight 20.8%, second-order transition temperature (DSC) :-25.9 DEG C; Mumber average molar mass M
n(GPC, PS standard): 210kg/mol; M
w/ M
n: 1.19; Mooney viscosity (ML 1+4, at 100 DEG C): 41ME
example 1c: synthesize by react with the chemical formula functionalized reagent that is (VII) and at the end of chain
the styrene-butadiene copolymer (comparison example) of functionalization
8.5kg hexane, 1185g 1 is filled in the reactor of the 20L of an inerting, 3-divinyl, 315g vinylbenzene, 8.2mmol 2, the n-Butyl Lithium of two (2-tetrahydrofuran base) propane of 2-and 10.55mmol, and these weighting materials are heated to 65 DEG C.Polyreaction carries out lasting 25 minutes under stirring at 65 DEG C.After this, add 10.55mmol (1.69ml) 2,2,4-trimethylammonium-[Isosorbide-5-Nitrae, 2] silicon for morpholine, and this reactor content is heated to 65 DEG C again continue 20 minutes.Subsequently, this rubber solutions discharged and pass through to add 3g's
1520 make it stablize, and by steam stripped by this solvent removal.By this buffings under reduced pressure 65 DEG C of dryings.
Contents of ethylene (IR spectrography): by weight 50.3%; Styrene content (IR spectrography): by weight 20.9%, second-order transition temperature (DSC) :-25.7 DEG C; Mumber average molar mass M
n(GPC, PS standard): 216kg/mol; M
w/ M
n: 1.18; Mooney viscosity (ML 1+4, at 100 DEG C): 44ME
example 1d: synthesize at the top of chain, there is tertiary amine group and chain end by with chemical formula
for the functionalized reagent of (VII) reacts and the styrene-butadiene copolymer of functionalization (of the present invention)
8.5kg hexane, 1185g 1 is filled in the reactor of the 20L of an inerting, 3-divinyl, 315g vinylbenzene, 11.3mmol 2,2-bis-(2-tetrahydrofuran base) propane, 14.1mmol Pyrrolizidine and 14.1mmol n-Butyl Lithium, and these weighting materials are heated to 65 DEG C.Polyreaction carries out lasting 25 minutes under stirring at 65 DEG C.After this, add 14.1mmol (2.26ml) 2,2,4-trimethylammonium-[Isosorbide-5-Nitrae, 2] silicon for morpholine, and this reactor content is heated to 65 DEG C again continue 20 minutes.Subsequently, this rubber solutions discharged and pass through to add 3g's
1520 make it stablize, and by steam stripped by this solvent removal.By this buffings under reduced pressure 65 DEG C of dryings.
Contents of ethylene (IR spectrography): by weight 49.3%; Styrene content (IR spectrography): by weight 20.3%, second-order transition temperature (DSC) :-26.3 DEG C; Mumber average molar mass M
n(GPC, PS standard): 170kg/mol; M
w/ M
n: 1.29; Mooney viscosity (ML 1+4, at 100 DEG C): 43ME
example 2a-d: rubber combination
The styrene-butadiene copolymer preparation of the rubber combination use-case 1a-1d of tire tread.
Composition is listed in Table 1.This rubber combination (sulphur removal and linking agent) is prepared in the kneader of 1.5L.Sulphur and promotor are mixed in cylinder at 40 DEG C subsequently.
example 3a-d: curing rubber performance
For determining the performance of curing rubber, the rubber combination in example 2a-d is continued 20 minutes 160 DEG C of solidifications.The performance of corresponding curing rubber as an example 3a-d is listed in table 2.
Use this curing rubber, determine following properties:
-at the elasticity of 60 DEG C (according to DIN 53512)
-wearing and tearing (according to DIN 53516)
-△ G*: the difference of viscoelastic modulus G* under 60 DEG C/1 hertz (MTS amplitude sweep) between 0.5% elongation and 15% elongation of dependent Frequency
-tan δ maximum value: the maximum dynamic antivibration in 60 DEG C/1 hertz viscoelastic modulus at dependent Frequency is measured, wherein tan δ=G "/G ' (MTS amplitude sweep)
Tan δ at-0 DEG C, 60 DEG C: from measurement (10Hz, the heating rate 1Kmin of the dynamic antivibration of the temperature dependent according to DIN 53513
-1), wherein tan δ=E "/E '
-elongation at break, the tensile stress (according to DIN 53504) during surrender
Elasticity when 60 DEG C, △ G*, tan δ maximum value (MTS) and 60 DEG C time tan δ be index (rolling resistance) as hysteresis loss during tire rolling.When 60 DEG C, elasticity is higher and △ G*, tan δ maximum value (MTS) and tan δ are lower, then the rolling resistance of tire is lower.When 0 DEG C, Tan δ is a metric of the wet and slippery dynamic resistance of tire.When 0 DEG C, this tan δ is higher, and the wet and slippery dynamic resistance of tire of expection is higher.
Tire applications needs low-rolling-resistance, this low-rolling-resistance elasticity when at 60 DEG C has high level and dynamic antivibration exists when high temperature (60 DEG C) has low tan δ value, and in curing rubber, measure low tan δ maximum value in MTS amplitude sweep.As clearly visible in table 2, the curing rubber of example 3d of the present invention be it should be noted that: have snappiness at 60 DEG C, has a low tan δ value and tan δ maximum value low in MTS amplitude sweep in the dynamic antivibration of 60 DEG C.
Tire applications needs low wet and slippery dynamic resistance in addition, and this low wet and slippery dynamic resistance exists when this curing rubber has high tan δ value in the dynamic antivibration of low temperature (0 DEG C).As clearly visible in table 2, the curing rubber of example 3d of the present invention be it should be noted that: in the dynamic antivibration of 0 DEG C, have a high tan δ value.
Claims (25)
1. diene polymer, is characterized in that this diene polymer has the tertiary amine group that chemical formula is (I) or (II) at the top of polymer chain
Or
Wherein
R
1, R
2identical or different, and each naturally may containing heteroatoms as the alkyl of O, N, S and/or Si, cycloalkyl, aryl, alkaryl and aromatic alkyl group,
Z is the organic group of a divalence, and this organic group can also comprise heteroatoms except C and H, as O, N, S and/or Si,
Further, at the end of polymer chain, there is the methanol-based containing silane that chemical formula is (III)
Or its metal-salt or its semi-metal salt, wherein
R
3, R
4, R
5, R
6identical or different, and each H naturally, may containing heteroatoms as the alkyl of O, N, S and/or Si, cycloalkyl, aryl, alkaryl and aromatic alkyl group,
A is the organic group of a divalence, and this organic group can also comprise heteroatoms except C and H, as O, N, S and/or Si.
2. according to the diene polymer described in claim 1, it is characterized in that this diene polymer polymer chain terminal, chemical formula is (III), methanol-based containing silane exists with the metallic salt form of chemical formula (IV)
Wherein
R
3, R
4, R
5, R
6identical or different, and each H naturally, may containing heteroatoms as the alkyl of O, N, S and/or Si, cycloalkyl, aryl, alkaryl and aromatic alkyl group,
A is the organic group of a divalence, and this organic group can also comprise heteroatoms except C and H, as O, N, S and/or Si,
N is the integer from 1 to 4,
M to be valency be 1 to 4 a kind of metal or semi-metal, preferably Li, Na, K, Mg, Ca, Fe, Co, Ni, Al, Nd, Ti, Si and/or Sn.
3., according to the diene polymer described in claim 1 or 2, it is characterized in that this diene polymer is polyhutadiene, polyisoprene, butadiene isoprene copolymer, butadiene-styrene copolymer, isoprene styrene multipolymer or butadiene-isoprene-styrene terpolymer.
4. according to the diene polymer described in claim 1, it is characterized in that this diene polymer has 10 000g/mol to 2 000 000g/mol, preferably the average molar mass (number average number) of 100 000g/mol to 1 000000g/mol.
5. according to the diene polymer described in claim 1, it is characterized in that this diene polymer has-110 DEG C to+20 DEG C, preferably the second-order transition temperature of-110 DEG C to 0 DEG C.
6. according to the diene polymer described in claim 1, it is characterized in that this diene polymer has 10 to 200 mooney units, preferably the mooney viscosity [ML 1+4 (100 DEG C)] of 30 to 150 mooney units.
7. preparation is according to the method for the diene polymer described in claim 1, it is characterized in that the functionalized reagent for introducing functional group at the end of this polymer chain is one or more 1-oxa-s-2-sila naphthenic hydrocarbon, and use general formula to be that the alkali metal amide of the secondary organic amine of (V) or (VI) is at the top of this polymer chain introducing tertiary amine group
Or
Wherein
R
1, R
2identical or different, and each naturally may containing heteroatoms as the alkyl of O, N, S and/or Si, cycloalkyl, aryl, alkaryl and aromatic alkyl group,
Z is the organic group of a divalence, and this organic group can also comprise heteroatoms except C and H, as O, N, S and/or Si,
M is Li, Na, K.
8., according to the method described in claim 7, it is characterized in that these 1-oxa-s-2-sila naphthenic hydrocarbon is the compound with following general formula (VII)
Wherein
R
3, R
4, R
5, R
6identical or different, and each H naturally, may containing heteroatoms as the alkyl of O, N, S and/or Si, cycloalkyl, aryl, alkaryl and aromatic alkyl group,
A is the organic group of a divalence, and this organic group can also comprise heteroatoms except C and H, as O, N, S and/or Si.
9. according to the method preparing diene polymer described in claim 7, it is characterized in that by secondary organic amine and organic alkali metal compound in position or react in a kind of preliminary forming step be separated and obtain multiple alkali metal amide, and one or more 1-oxa-s-2-sila naphthenic hydrocarbon is used for the reaction with the reactive terminal of this polymer chain.
10., according to the method described in claim 7, it is characterized in that these 1-oxa-s-2-sila naphthenic hydrocarbon just adds after completion of the polymerization reaction.
11. according to the method described in claim 9, it is characterized in that this alkali metal amide is used as anionic polymerization initiator.
12. according to the method described in claim 9, it is characterized in that this secondary organic amine used is Pyrrolizidine or hexamethylene imine, and this organic alkali metal compound is butyllithium.
13. according to the method described in claim 9, it is characterized in that the molar weight of secondary amine is less than or equal to the molar weight of organic alkali metal compound, this mol ratio preferably 0.05-2.00:0.05-2.00.
14. according to the method described in claim 7, it is characterized in that the amount based on the polymkeric substance with polymer chain reaction end, the amount of 1-oxa--2-sila naphthenic hydrocarbon is by weight between 0.005% to 2%, preferably by weight between 0.01% to 1%.
15. according to the method described in claim 7, it is characterized in that coupling reagent being used for reaction.
16. purposes of diene polymer in production curable rubber compositions according to any one of claim 1-6.
17. according to the obtainable curable rubber compositions of claim 16, it is characterized in that they comprise aging stabilizer, oil, weighting agent, rubber and/or rubber ingredients.
18. curable rubber compositions, comprise according to the diene polymer described in claim 1 or 2.
19. curable rubber compositions, comprise the diene polymer according to the functionalization described in claim 1, this diene polymer has the tertiary amine group that chemical formula is (I) or (II) at the top of polymer chain, and has the functional group of chemical formula for (III) at the end of polymer chain.
20. curable rubber compositions, the diene polymer of the functionalization comprised, it is the tertiary amine group of (I) or (II) that this diene polymer has according to the chemical formula described in claim 1 at the top of polymer chain, and to have according to the chemical formula described in claim 2 at the end of polymer chain be the functional group of (IV).
21. curable rubber compositions, comprise the diene polymer of functionalization, it is the tertiary amine group of (I) or (II) that this diene polymer has according to the chemical formula described in claim 1 at the top of polymer chain, and to have according to the chemical formula described in claim 1 and 2 at the end of polymer chain be the functional group of (III) and (IV).
22. are producing the purposes in tire, particularly tire tread according to claim 19 to this curable rubber compositions according to any one of 21.
23. are producing purposes, particularly cable sheath in moulded product, flexible pipe, pulley belt, travelling belt, pressure roller coating, sole, sealing-ring and damper assembly according to claim 19 to the curable rubber compositions according to any one of 21.
24. according to tire obtainable in claim 22.
25. according to moulded product obtainable in claim 23.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20120167353 EP2662406A1 (en) | 2012-05-09 | 2012-05-09 | Carbinol-terminated polymers containing amine |
| EP12167353.7 | 2012-05-09 | ||
| PCT/EP2013/058882 WO2013167411A1 (en) | 2012-05-09 | 2013-04-29 | Carbinol-terminated polymers containing amine |
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| CN104271657B CN104271657B (en) | 2016-10-12 |
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|---|---|
| US (1) | US9718913B2 (en) |
| EP (2) | EP2662406A1 (en) |
| JP (1) | JP6215310B2 (en) |
| KR (1) | KR102051426B1 (en) |
| CN (1) | CN104271657B (en) |
| BR (1) | BR112014027915B1 (en) |
| ES (1) | ES2663676T3 (en) |
| HK (1) | HK1208487A1 (en) |
| HU (1) | HUE037537T2 (en) |
| IN (1) | IN2014DN09296A (en) |
| MX (1) | MX360131B (en) |
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| PL (1) | PL2847264T3 (en) |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9090730B1 (en) * | 2014-08-19 | 2015-07-28 | The Goodyear Tire & Rubber Company | Rubber composition and pneumatic tire |
| WO2018088483A1 (en) * | 2016-11-14 | 2018-05-17 | 日本ゼオン株式会社 | Method for producing modified conjugated diene rubber |
| US10730985B2 (en) | 2016-12-19 | 2020-08-04 | Bridgestone Corporation | Functionalized polymer, process for preparing and rubber compositions containing the functionalized polymer |
| WO2019118688A1 (en) | 2017-12-15 | 2019-06-20 | Bridgestone Corporation | Functionalized polymer, process for preparing and rubber compositions containing the functionalized polymer |
| US11208518B2 (en) | 2018-12-11 | 2021-12-28 | The Goodyear Tire & Rubber Company | Functionalized polymer, rubber composition and pneumatic tire |
| EP4217208A1 (en) | 2020-09-28 | 2023-08-02 | ARLANXEO Deutschland GmbH | Partially hydrogenated diene polymers |
| WO2023104784A1 (en) | 2021-12-07 | 2023-06-15 | Arlanxeo Deutschland Gmbh | Diene rubbers prepared with unsaturated siloxane-based coupling agents |
| WO2023152146A1 (en) | 2022-02-11 | 2023-08-17 | Arlanxeo Deutschland Gmbh | Modified diene rubbers |
| WO2023193943A1 (en) | 2022-04-08 | 2023-10-12 | Arlanxeo Deutschland Gmbh | Branched modified diene rubbers |
| WO2023247719A1 (en) | 2022-06-23 | 2023-12-28 | Arlanxeo Deutschland Gmbh | Alpha-omega-functionalized polymers |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5290901A (en) * | 1993-06-14 | 1994-03-01 | Dow Corning Corporation | Method for preparation of carbinol-functional siloxanes |
| EP0594107A1 (en) * | 1992-10-19 | 1994-04-27 | Bridgestone Corporation | Process for preparing a polymer using lithium initiator prepared by in situ preparation |
| CN101671418A (en) * | 2008-08-27 | 2010-03-17 | 住友化学株式会社 | Conjugated diene polymer, conjugated diene polymer composition, and method for producing conjugated diene polymer |
| CN102083889A (en) * | 2008-04-30 | 2011-06-01 | 株式会社普利司通 | Process for production of modified conjugated diene copolymer, modified conjugated diene copolymer produced by the process, rubber composition, and tire |
| CN102186887A (en) * | 2008-10-16 | 2011-09-14 | 朗盛德国有限责任公司 | Functionalized diene rubbers |
Family Cites Families (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3244664A (en) | 1960-10-24 | 1966-04-05 | Phillips Petroleum Co | Silicon-containing polymers |
| GB1597500A (en) | 1977-12-29 | 1981-09-09 | Shell Int Research | Polymers |
| US4417029A (en) | 1981-08-03 | 1983-11-22 | Atlantic Richfield Company | Derivatization of star-block copolymers |
| JPS61103903A (en) * | 1984-10-26 | 1986-05-22 | Nippon Zeon Co Ltd | Production of diene polymer rubber |
| US4616069A (en) | 1984-10-26 | 1986-10-07 | Nippon Zeon Co., Ltd. | Process for making diene polymer rubbers |
| US4618650A (en) | 1985-09-04 | 1986-10-21 | The Goodyear Tire & Rubber Company | Siloxane containing network polymer |
| GB9002804D0 (en) | 1990-02-08 | 1990-04-04 | Secr Defence | Anionic polymerisation |
| US5665829A (en) | 1990-02-08 | 1997-09-09 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Gt. Britain & Northern Ireland | Process for the polymerization of olefinic-containing monomers employing anionic initiators |
| US5332810A (en) | 1992-10-02 | 1994-07-26 | Bridgestone Corporation | Solubilized anionic polymerization initiator and preparation thereof |
| US6025450A (en) | 1992-10-02 | 2000-02-15 | Bridgestone Corporation | Amine containing polymers and products therefrom |
| US5625017A (en) | 1992-10-19 | 1997-04-29 | Bridgestone Corporation | Process for preparing a polymer using lithium initiator prepared by in situ preparation |
| US5416168A (en) | 1994-03-31 | 1995-05-16 | Shell Oil Company | Protected functional initiators for making terminally functionalized polymers |
| US5521309A (en) | 1994-12-23 | 1996-05-28 | Bridgestone Corporation | Tertiary-amino allyl-or xylyl-lithium initiators and method of preparing same |
| US5574109A (en) * | 1995-02-01 | 1996-11-12 | Bridgestone Corporation | Aminoalkyllithium compounds containing cyclic amines and polymers therefrom |
| US5496940A (en) | 1995-02-01 | 1996-03-05 | Bridgestone Corporation | Alkyllithium compounds containing cyclic amines and their use in polymerization |
| FR2740778A1 (en) | 1995-11-07 | 1997-05-09 | Michelin & Cie | SILICA-BASED RUBBER COMPOSITION AND FUNCTIONALIZED DIENE POLYMER HAVING TERMINAL SILANOL FUNCTION |
| JP3622803B2 (en) | 1995-11-28 | 2005-02-23 | 日本ゼオン株式会社 | Rubber composition |
| US5659056A (en) | 1996-04-10 | 1997-08-19 | Bridgestone Corporation | Stabilization of siloxane terminated polymers |
| US6384117B1 (en) | 1997-07-11 | 2002-05-07 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US6008295A (en) | 1997-07-11 | 1999-12-28 | Bridgestone Corporation | Diene polymers and copolymers incorporating partial coupling and terminals formed from hydrocarboxysilane compounds |
| US6255404B1 (en) | 1999-07-26 | 2001-07-03 | Bridgestone Corporation | Method to control increase in viscosity during aging of siloxane modified polymers |
| US6279632B1 (en) | 1999-11-24 | 2001-08-28 | Bridgestone Corporation | Method to control increase in viscosity during aging of siloxane modified polymers |
| FR2854404B1 (en) * | 2003-04-29 | 2005-07-01 | Michelin Soc Tech | METHOD OF OBTAINING GRAFT ELASTOMER WITH FUNCTIONAL GROUPS ALONG THE CHAIN AND RUBBER COMPOSITIONS |
| TWI385182B (en) | 2004-03-15 | 2013-02-11 | Jsr Corp | Conjugated diene (co) poly rubber and method for producing the same |
| US7868081B2 (en) * | 2005-03-04 | 2011-01-11 | Bridgestone Corporation | Rubber composition and tire using same |
| CN101466783B (en) * | 2006-04-13 | 2012-05-09 | 株式会社普利司通 | Composition including multiple functionalized polymers |
| JP5391557B2 (en) * | 2007-02-28 | 2014-01-15 | 住友化学株式会社 | Conjugated diene polymer, process for producing conjugated diene polymer, and conjugated diene polymer composition |
| US8063165B2 (en) | 2007-06-18 | 2011-11-22 | Bridgestone Corporation | Functional polymers prepared with sulfur-containing initiators |
| JP5297888B2 (en) * | 2009-05-20 | 2013-09-25 | 株式会社ブリヂストン | Modifier, modified conjugated diene polymer production method, modified conjugated diene polymer, rubber composition, and pneumatic tire |
| EP2452951A1 (en) * | 2010-11-16 | 2012-05-16 | LANXESS Deutschland GmbH | Carbinol-terminated polymers containing silane |
| EP2662392A1 (en) * | 2012-05-09 | 2013-11-13 | LANXESS Deutschland GmbH | Carbinol-terminated polymers containing allylamine |
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2012
- 2012-05-09 EP EP20120167353 patent/EP2662406A1/en not_active Withdrawn
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2013
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0594107A1 (en) * | 1992-10-19 | 1994-04-27 | Bridgestone Corporation | Process for preparing a polymer using lithium initiator prepared by in situ preparation |
| US5290901A (en) * | 1993-06-14 | 1994-03-01 | Dow Corning Corporation | Method for preparation of carbinol-functional siloxanes |
| CN102083889A (en) * | 2008-04-30 | 2011-06-01 | 株式会社普利司通 | Process for production of modified conjugated diene copolymer, modified conjugated diene copolymer produced by the process, rubber composition, and tire |
| CN101671418A (en) * | 2008-08-27 | 2010-03-17 | 住友化学株式会社 | Conjugated diene polymer, conjugated diene polymer composition, and method for producing conjugated diene polymer |
| CN102186887A (en) * | 2008-10-16 | 2011-09-14 | 朗盛德国有限责任公司 | Functionalized diene rubbers |
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| CN104271657B (en) | 2016-10-12 |
| US9718913B2 (en) | 2017-08-01 |
| HK1208487A1 (en) | 2016-03-04 |
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| ES2663676T3 (en) | 2018-04-16 |
| PL2847264T3 (en) | 2018-07-31 |
| HUE037537T2 (en) | 2018-09-28 |
| TW201412799A (en) | 2014-04-01 |
| JP2015521221A (en) | 2015-07-27 |
| MX360131B (en) | 2018-10-23 |
| MX2014013691A (en) | 2015-02-05 |
| EP2847264B1 (en) | 2018-02-21 |
| EP2662406A1 (en) | 2013-11-13 |
| IN2014DN09296A (en) | 2015-07-10 |
| BR112014027915B1 (en) | 2021-02-23 |
| TWI599588B (en) | 2017-09-21 |
| KR102051426B1 (en) | 2019-12-03 |
| BR112014027915A2 (en) | 2017-06-27 |
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